CN112447980B - Electrolytic copper foil, electrode comprising same and lithium ion battery - Google Patents

Electrolytic copper foil, electrode comprising same and lithium ion battery Download PDF

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CN112447980B
CN112447980B CN201910836372.0A CN201910836372A CN112447980B CN 112447980 B CN112447980 B CN 112447980B CN 201910836372 A CN201910836372 A CN 201910836372A CN 112447980 B CN112447980 B CN 112447980B
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electrolytic copper
copper foil
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lithium ion
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CN112447980A (en
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黄建铭
赖耀生
周瑞昌
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Chang Chun Petrochemical Co Ltd
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Chang Chun Petrochemical Co Ltd
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C23C22/26—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
    • C23C22/27—Acids
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
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    • H01M4/64—Carriers or collectors
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    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
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    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
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Abstract

The invention provides an electrolytic copper foil, an electrode containing the electrolytic copper foil and a lithium ion battery. The electrolytic copper foil has a chromium adhesion amount of 15 μ g/dm for the first chromium layer and the second chromium layer2To 50. mu.g/dm2The oxalic acid contact angles of the first surface and the second surface are 15-50 degrees, the brightness of the first surface and the second surface is 17.5-40 and 38-60 respectively, and the resistivity of the first surface and the second surface is 1.72 mu omega cm-2.25 mu omega cm, so that the electrolytic copper foil has good weather resistance, the electrolytic copper foil and the active material have good adhesion strength, and the cycle life performance of the lithium ion battery is optimized.

Description

Electrolytic copper foil, electrode comprising same and lithium ion battery
Technical Field
The present invention relates to an electrolytic copper foil, and more particularly to an electrolytic copper foil for a lithium ion battery. In addition, the invention also relates to an electrode and a lithium ion battery containing the electrolytic copper foil.
Background
With the popularization of Portable Electronic Devices (PEDs), Electric Vehicles (EVs), and Hybrid Electric Vehicles (HEVs), lithium ion batteries having the advantages of high power density, fast charging, no memory effect, etc. are actively being developed to meet the market demand of the rapid development nowadays.
The lithium ion battery completes charging and discharging work by shuttling lithium ions back and forth between a positive electrode and a negative electrode. Electrodes for lithium ion batteries are typically made by coating a slurry containing the active material on a metal foil. Lithium ion batteries can be classified into lithium cobalt batteries (LiCoO) according to their materials2cell), lithium nickel battery (LiNiO)2cell), lithium manganese battery (LiMn)2O4cell), lithium cobalt nickel battery (LiCo)XNi1-XO2cell) and lithium iron phosphate battery (LiFePO)4cell), and the like.
Electrodes of lithium ion batteries are usually made by coating slurry containing active materials on both surfaces of copper foil, so the characteristics and quality of copper foil have a great influence on the performance of lithium ion batteries. For example, in the process of charging and discharging of a lithium ion battery, the active material in the negative electrode inevitably expands and contracts; the existing copper foil and the negative active material lack good adhesion strength, so that the negative active material is easy to peel or fall off from the surface of the copper foil in the charging and discharging processes, and the cycle life performance of the lithium ion battery is further shortened.
Disclosure of Invention
In view of the above, an object of the present invention is to improve and reduce the phenomenon that an electrode active material is easily peeled or dropped from the surface of a copper foil during charging and discharging, thereby improving the cycle life performance of a lithium ion battery.
In order to achieve the above objects, the present invention provides an electrolytic copper foil comprising a copper layer, a first chromium layer and a second chromium layer; the copper layer comprises a deposition surface and a roller surface on opposite sides; the first chromium layer is formed on a deposition surface of the copper layer, the first chromium layer including a first surface opposite to the deposition surface, the first chromium layer having a chromium adhesion amount of 15 micrograms/square decimeter (μ g/dm) or more2) And less than or equal to 50 [ mu ] g/dm2And a contact angle between the first surface of the first chromium layer and a 0.1 weight percent (wt%) aqueous solution of oxalic acid is greater than or equal to 15 degrees and less than or equal to 50 degrees, a lightness of the first surface of the first chromium layer is greater than or equal to 17.5 and less than or equal to 40, and a resistivity of the first surface of the first chromium layer is greater than or equal to 1.72 μ Ω · cm and less than or equal to 2.25 μ Ω · cm; and a second chromium layer formed on the cylindrical surface of the copper layer, the second chromium layer including a second surface opposite to the cylindrical surface, the second chromium layer having a chromium adhesion amount of 15 [ mu ] g/dm or more2And less than or equal to 50 [ mu ] g/dm2A contact angle between the second surface of the second chromium layer and 0.1 wt% of oxalic acid aqueous solution is more than or equal to 15 DEGAnd less than or equal to 50 degrees, a lightness of the second surface of the second chromium layer is greater than or equal to 38 and less than or equal to 60, and a resistivity of the second surface of the second chromium layer is greater than or equal to 1.72 [ mu ] Ω & cm and less than or equal to 2.25 [ mu ] Ω & cm.
According to the invention, the weather resistance of the electrolytic copper foil and the bonding strength between the electrolytic copper foil and the active material can be specifically improved by simultaneously regulating and controlling the chromium adhesion amount of the first chromium layer and the second chromium layer in the electrolytic copper foil, the contact angle between the first surface and the second surface and 0.1 wt% oxalic acid aqueous solution, the lightness of the first surface and the second surface, the resistivity of the first surface and the second surface of the second chromium layer, and the like, so that the cycle life of the lithium ion battery containing the electrolytic copper foil is prolonged.
In this specification, a copper layer of an electrolytic copper foil is obtained by using a copper electrolyte solution containing sulfuric acid and copper sulfate as main components, a titanium plate coated with iridium or an oxide thereof as an insoluble anode (DSA), and a titanium roll as a cathode roll (cathode drum) and passing a direct current between the two electrodes to electrolytically precipitate copper ions in the copper electrolyte solution and deposit the copper ions on the cathode roll, followed by peeling and winding; the copper layer includes two surfaces on opposite sides, the surface of the copper layer near the cathode roll in the process is called "roll side", and the surface of the copper layer near the copper electrolyte in the process is called "deposited side".
In the present specification, the color of the first surface of the first chrome layer and the second surface of the second chrome layer is defined according to the color system L a b as specified by the Commission international de L' Eclairage (CIE). The "lightness" means L defined based on L a b color system, the higher the lightness value is, the brighter the color of the surface is, the closer to white the color is; the "chromaticity a value" means a defined based on L a b color system, the lower the value a, the closer the color of the surface is to green, and the higher the value a, the closer the color of the surface is to red; the "chromaticity b value" means b defined based on the color system of L a b, the lower the b value, the closer the color of the surface is to blue, and the higher the b value, the closer the color of the surface is to yellow.
Preferably, the brightness of the first surface of the electrolytic copper foil of the present invention may be greater than or equal to 25 and less than or equal to 40, and the brightness of the second surface may be greater than or equal to 45 and less than or equal to 60. Therefore, when the electrolytic copper foil is applied to the lithium ion battery, the charge-discharge cycle life performance of the lithium ion battery can be further optimized.
Preferably, the contact angle between the first surface of the electrolytic copper foil of the present invention and a 0.1 wt% oxalic acid aqueous solution may be greater than or equal to 15 degrees and less than 40 degrees, and the contact angle between the second surface and a 0.1 wt% oxalic acid aqueous solution may be greater than or equal to 15 degrees and less than or equal to 40 degrees. More preferably, the contact angle between the first surface of the electrolytic copper foil of the present invention and a 0.1 wt% aqueous oxalic acid solution may be greater than or equal to 15 degrees and less than or equal to 30 degrees, and the contact angle between the second surface and a 0.1 wt% aqueous oxalic acid solution may be greater than or equal to 15 degrees and less than or equal to 30 degrees. Accordingly, when the electrolytic copper foil of the present invention is applied to a lithium ion battery, the adhesion strength between the electrolytic copper foil and an active material can be further improved.
Preferably, in the electrodeposited copper foil of the present invention, the chromaticity a value of the first surface may be greater than or equal to 3 and less than or equal to 12, and the chromaticity a value of the second surface may be greater than or equal to 8 and less than or equal to 16.
Preferably, the chromaticity b value of the first surface is greater than or equal to 1.3 and less than or equal to 18, and the chromaticity b value of the second surface is greater than or equal to 8 and less than or equal to 16.
In addition, the invention also provides an electrode of a lithium ion battery, which comprises the electrolytic copper foil.
According to the invention, the electrolytic copper foil can be used as a negative electrode of a lithium ion battery and can also be used as a positive electrode of the lithium ion battery. The electrolytic copper foil is suitable for use as a current collector, and is coated with at least one layer of an active material on one or both sides to make an electrode.
The active material can provide the electrode with good cycle characteristics. For example, the active material can be a carbon material, a silicon-carbon composite material, a metal oxide, a metal alloy or a polymer, wherein the carbon material or the silicon material is preferred, but not limited thereto. Specifically, the carbon material may be non-graphitic carbon (non-graphite carbon), coke (coke), graphite (graphite), glassy carbon (glass carbon), carbon fiber (carbon fiber), activated carbon (activated carbon), carbon black (carbon black), or a high polymer calcined material, but is not limited thereto; wherein the coke comprises pitch coke, needle coke or petroleum coke; the high polymer calcined material is obtained by firing a high polymer material such as phenol-formaldehyde resin (phenol-formaldehyde resin) or furan resin (furan resin) at an appropriate temperature so as to be carbonated. The silicon material can be used as a negative electrode active material having an excellent ability to form an alloy together with lithium ions and an excellent ability to extract lithium ions from the alloy lithium, and when the silicon material is used to form a lithium ion secondary battery, a secondary battery having a large energy density can be realized; the silicon material may be used In combination with cobalt (Co), iron (Fe), tin (Sn), nickel (Ni), copper (Cu), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), chromium (Cr), ruthenium (Ru), molybdenum (Mo), or combinations thereof to form an alloy material. The elements of the metal or metal alloy may be selected from the group consisting of: cobalt, iron, tin, nickel, copper, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, chromium, ruthenium, and molybdenum, but are not limited thereto. Examples of the metal oxide are, but not limited to, iron sesquioxide, iron tetraoxide, ruthenium dioxide, molybdenum dioxide, and molybdenum trioxide. Examples of such polymers are polyacetylene (polyacetylene) and polypyrrole (polypyrrole), but are not limited thereto.
Furthermore, the invention also provides a lithium ion battery which comprises the electrolytic copper foil. The lithium ion battery includes: a positive electrode, a negative electrode and an electrolyte. In some embodiments, the lithium ion battery may be separated between the positive electrode and the negative electrode by a separator.
According to the present invention, the electrolyte may include a solvent, an electrolyte, or an additive added as the case may be. The solvent in the electrolyte includes a non-aqueous solvent such as: cyclic carbonates such as Ethylene Carbonate (EC) and Propylene Carbonate (PC); chain carbonates such as dimethyl Carbonate (DMC), diethyl Carbonate (DEC) and Ethyl Methyl Carbonate (EMC); or sultone, but is not limited thereto; the above solvents may be used alone or in combination of two or more solvents.
The lithium ion battery (also referred to as a lithium ion secondary battery) may be a stack type lithium ion battery including a negative electrode and a positive electrode stacked via a separator, or a spirally wound stack type lithium ion battery including a continuous electrode and a separator spirally wound together, without particular limitation. For example, the lithium ion battery applied to a notebook type personal computer may be made into a cylinder type secondary battery, and the lithium ion battery applied to a mobile phone may be made into a rectangular parallelepiped type secondary battery, a button type secondary battery or a coin type secondary battery, without particular limitation.
Drawings
FIG. 1 is a schematic view showing a production flow of an electrolytic copper foil.
FIG. 2 is a schematic side view of an electrolytic copper foil.
Description of the symbols
10 electrolytic deposition device 11 cathode roller 12 insoluble anode 13 copper electrolyte
14 pan feeding pipe 20 sprinkler 21 sprays liquid 30 surface treatment device
31 treatment tank 32 polar plate 41 first guide roller 42 second guide roller
43 third guide roll 44 fourth guide roll 50 electrolytic copper foil 51 copper layer
511 depositing a 512 roll surface 52 a first chromium layer 521 a first surface
53 second chrome layer 531 second surface I polar plate polar distance
Detailed Description
Hereinafter, embodiments of the electrolytic copper foil, the electrode and the lithium ion battery according to the present invention will be described with reference to several examples, and several comparative examples will be provided as a control. It is to be understood that the examples set forth herein are presented by way of illustration only of embodiments of the present invention and are not intended to limit the scope of the invention, which is to be construed as broadly as the present invention may be modified and varied by those skilled in the art without departing from the spirit of the invention in its broadest form.
Electrolytic copper foil
Examples 1 to 11: electrolytic copper foil
Examples 1 to 11 electrolytic copper foils were produced by using the production apparatus shown in FIG. 1 and successively passing through substantially the same pre-bath spraying step, electrolytic deposition step and rust-preventive treatment step. The differences of examples 1 to 11 mainly lie in the process parameters set in the pre-tank spraying step and the rust inhibitive treatment step and the composition of the chromium rust inhibitive solution.
As shown in FIG. 1, the apparatus for producing an electrolytic copper foil comprises an electrolytic deposition device 10, a spraying device 20, a surface treatment device 30 and a series of guide rolls; the electrowinning apparatus 10 includes a cathode drum 11, an insoluble anode 12, a copper electrolyte 13, and a feed pipe 14. Cathode roll 11 is rotatable and includes a surface that can be selectively mechanically polished by a polishing wheel (not shown). Insoluble anode 12 is disposed below cathode drum 11, substantially around the lower half of cathode drum 11. The cathode drum 11 and the insoluble anode 12 are spaced apart from each other and receive a copper electrolyte 13 fed from a feed pipe 14. A plurality of feeding holes (not shown) are formed in the feeding pipe 14 at intervals; the spraying device 20 is arranged at a position which is 5 cm away from the cathode roller 11; the surface treatment device 30 includes a treatment tank 31 and a pole plate 32 disposed therein; the series of guide rollers includes a first guide roller 41, a second guide roller 42, a third guide roller 43, and a fourth guide roller 44, which are used to transport the electrodeposited original foil, the surface-treated copper foil, and the finished product, and finally to wind the electrodeposited copper foil 50 on the fourth guide roller 44.
The method for manufacturing the electrolytic copper foils of examples 1 to 11 using the apparatus for manufacturing an electrolytic copper foil shown in FIG. 1 will be collectively described as follows:
firstly, preparing a copper electrolyte for an electrolytic deposition step, wherein the formula of the copper electrolyte is as follows:
copper sulfate (CuSO)4·5H2O): 320 grams per liter (g/L),
Sulfuric acid: 110g/L,
Low molecular weight bone cement (SV, available from Nippi inc., molecular weight between 4000 and 7000 Da): 5.5 milligrams per liter (mg/L),
Sodium 3-mercapto-1-propanesulfonate (sodium 3-mercapto-1-propanesulfonate, MPS, available from auto-polymerization and international co., ltd): 3mg/L,
Hydrochloric acid (purchased from RCI Labscan Ltd.): 25mg/L,
Thiourea (from Panreac quiimica Sau): 0.01 mg/L.
The prepared copper electrolyte is used in the electrolytic deposition step and is also used as a spraying liquid in the spraying step before the tank, and the formula of the copper electrolyte used in the two steps is the same.
When the step of electrolytic deposition is performed, the spraying device 20 is adjusted to be about 5 centimeters away from the cathode roller 11, the spraying angle is 45 degrees, and the copper electrolyte (i.e., the spraying liquid 21) with the temperature of 50 ℃ and the flow rate of 5 liters/minute (L/min) to 10L/min is sprayed on the surface of the cathode roller 11 which is not immersed in the copper electrolyte 13 in a parabolic spraying manner. The temperature of the copper electrolyte 13 was controlled to 50 ℃ and a current density of 50 amperes per square decimeter (A/dm) was applied to the cathode roll 11 and the insoluble anode 122) So that copper ions in copper electrolyte 13 are electrodeposited on the surface of cathode drum 11 to form a raw foil, and then the raw foil is peeled from cathode drum 11 and guided to first guide roller 41.
Subsequently, the raw foil is conveyed to the surface treatment device 30 by the first guide roller 41 and the second guide roller 42 to be subjected to rust prevention treatment. The base foil is immersed in a treatment bath 31 filled with a chromium rust preventive solution, and is subjected to electrodeposition to form a chromium layer.
The formula of the chromium antirust liquid and the technological conditions of the antirust treatment are as follows:
oxalic acid: 0g/L to 1.0g/L,
Chromic acid (CrO 3): 1.0 to 2.0g/L,
Surfactant (Triton X-100, from Sigma-Aldrich): 0g/L to 1.0g/L,
Liquid temperature: at 25 deg.C,
Current density: 0.5A/dm2To 1.5A/dm2、
Treatment time: 5 seconds,
Distance between the pole plate 32 and the original foil (pole plate distance I for short): 10 millimeters (mm) to 15 mm.
After the rust-preventive treatment under the above conditions, the raw foil subjected to the rust-preventive treatment is guided to the third guide roller 43 to be dried, and is wound on the fourth guide roller 44 to obtain an electrolytic copper foil 50 having a thickness of about 8 μm.
According to the above-mentioned production methods, the electrolytic copper foils of examples 1 to 11 can be produced, respectively. As shown in fig. 2, the electrolytic copper foil 50 of each example includes a copper layer 51 (corresponding to the above-described raw foil which has not been subjected to the rust-proofing treatment step), a first chromium layer 52, and a second chromium layer 53. The copper layer 51 includes a deposition surface 511 and a roll surface 512 on opposite sides. The first chromium layer 52 is formed on the deposition surface 511 of the copper layer 51 and includes a first surface 521 opposite to the deposition surface 511. A second chromium layer 53 is then formed on the roll surface 512 of the copper layer 51, the second chromium layer 53 comprising a second surface 531 opposite the roll surface 512.
In the above process, the flow rates set in the pre-tank spraying step, the current densities and the plate pitch set in the rust preventing treatment step, and the formulations of the chromium rust preventing solutions in each of examples 1 to 11 are shown in table 1.
In the surface treatment step, in addition to the above-described rust prevention treatment step, in another embodiment, after the raw foil is peeled off from the cathode roll, another surface treatment such as roughening treatment or passivation treatment may be performed by connecting another surface treatment apparatus in series as appropriate to adjust the characteristics of the electrolytic copper foil. At this time, the two outermost opposite sides of the original foil which is first subjected to other surface treatment are the deposition surface and the roll surface, respectively.
Comparative examples 1 to 11: electrolytic copper foil
Comparative examples 1 to 11 were comparison examples 1 to 11, which produced electrolytic copper foils substantially in the same manner as in examples 1 to 11, but did not control the spray parameters and the formulation and parameters of the chromium anticorrosive solution for anticorrosive treatment appropriately. The process conditions for each comparative example different from the above examples are also shown in table 1; as described above, the electrolytic copper foils of comparative examples 1 to 11 are also shown in FIG. 2.
Table 1: spraying parameters set in the pre-time-slot spraying step of the electrolytic copper foils of examples 1 to 11(E1 to E11) and comparative examples 1 to 11(C1 to C11) and the formulation and process parameters of the chromium anticorrosive solution used in the anticorrosive treatment step were prepared
Figure GDA0003217071480000071
Figure GDA0003217071480000081
Test example 1: oxalic acid contact angle
First, 0.1g of oxalic acid was placed in a beaker, and water was added until the total solution weight reached 100g, to prepare a 0.1 wt% oxalic acid aqueous solution. Then, the electrolytic copper foil is placed into a hand-held contact angle measuring instrument (instrument model: Phoenixi, available from Surface Electro Optics), the height of the mouth of the titrator from about 2mm to the Surface of the electrolytic copper foil is adjusted, then a titration knob on the titrator is rotated, the 0.1 wt% oxalic acid aqueous solution is drawn up until a drop of about 10 microliters (muL) to 15 muL is dripped out on the Surface of the electrolytic copper foil, and the contact angle of the electrolytic copper foil is further measured.
Contact angles between the first and second surfaces of the electrolytic copper foils of examples 1 to 11 and comparative examples 1 to 11, respectively, and a 0.1 wt% aqueous oxalic acid solution were measured in the above-described manner, and the results thereof are shown in table 2.
Test example 2: l a b
In this test example, the electrodeposited copper foils of examples 1 to 11 and comparative examples 1 to 11 were used as test subjects, and the reflected lights from the first and second surfaces of each electrodeposited copper foil were measured with a spectrophotometer (model CM-2500c, available from Konica Minolta) under a light source of D65 sunlight at an observation angle of 2 ° in accordance with the color standard of CIE 1976, and converted into L a b three-dimensional space, and the lightness (L) and the chromaticity a, b values of the first and second surfaces of each electrodeposited copper foil were recorded, and the results are also shown in table 2.
Test example 3: resistivity of
In this test example, the electrolytic copper foils (100 mm. times.100 mm in size) of examples 1 to 11 and comparative examples 1 to 11 were used as test subjects, and the resistivity of each of the electrolytic copper foils on the first surface and the second surface was measured under the conditions of a gauge diameter of 100 μm and a gauge length of 1.6mm by a four-point probe measurement system (model LRS4-TG2, available from Kaisinglong science and technology Co., Ltd.) by a measurement method of IPC-TM-6502.5.14. The resistivity scaling factor was 4.532, the results of which are also shown in Table 2.
Test example 4: amount of chromium deposited
In this test example, the electrolytic copper foils (each 100mm × 100mm in size) of examples 1 to 11 and comparative examples 1 to 11 were used as test subjects, a protective coating was applied to the second surface of each electrolytic copper foil to prevent the second chromium layer from being dissolved by the hydrochloric acid aqueous solution, the electrolytic copper foils were immersed in 20ml of 18 wt% hydrochloric acid aqueous solution at room temperature for 10 minutes to completely dissolve the first chromium layer, the aqueous solution in which the first chromium layer was dissolved was measured by an inductively coupled plasma atomic emission spectrometer (ICP-OES, instrument model ICP: ICP7000, available from ThermoFisher), and the chromium adhesion amount was analyzed under the conditions of argon as a carrier gas and an atomizer flow rate of 0.5L/min.
Similarly, the electrodeposited copper foils of examples 1 to 11 and comparative examples 1 to 11 having the same size were used as test subjects, a protective coating was applied on the first surface of each electrodeposited copper foil to prevent the first chromium layer from being dissolved by the hydrochloric acid aqueous solution, the electrodeposited copper foils were continuously immersed in 20ml of 18 wt% hydrochloric acid aqueous solution at room temperature for 10 minutes to completely dissolve the second chromium layer, the above-mentioned aqueous solutions in which the second chromium layer was dissolved were measured by ICP-OES, and the amount of chromium attached to the second chromium layer was analyzed under the conditions of argon as a carrier gas and an atomizer flow rate of 0.5L/min.
The results of analyzing the chromium adhesion amounts of the first chromium layer and the second chromium layer of each of the electrodeposited copper foils are also shown in Table 2.
Test example 5: weather resistance
In this test example, the electrolytic copper foils of examples 1 to 11 and comparative examples 1 to 11 were used as test subjects, and each electrolytic copper foil was placed in a constant temperature and humidity oven at a temperature of 70 ℃ and a relative humidity of 80% for 15 hours, and then three testers visually observed whether the surface of the electrolytic copper foil was discolored or white or black spots were generated to evaluate the weather resistance. If no obvious discoloration, white point or black point generation is observed after the electrolytic copper foil is placed in the oven, the electrolytic copper foil is marked with O in the table 2, which indicates that the electrolytic copper foil has good weather resistance; if discoloration or generation of white or black spots is observed after the electrodeposited copper foil is placed in an oven, it is marked with "X" in table 2, indicating that the electrodeposited copper foil is poor in weather resistance.
Discussion of characteristics of electrolytic copper foil
The electrolytic copper foils of examples 1 to 11 simultaneously had the following characteristics:
(1) the chromium adhesion amount of the first chromium layer was 15. mu.g/dm2To 50. mu.g/dm2The chromium adhesion amount of the second chromium layer was 15. mu.g/dm2To 50. mu.g/dm2；
(2) The contact angles between the first surface of the first chromium layer and the second surface of the second chromium layer and 0.1 weight percent of oxalic acid aqueous solution are 15-50 degrees;
(3) a lightness of the first surface of the first chromium layer is greater than or equal to 17.5 and less than or equal to 40, and a lightness of the second surface of the second chromium layer is greater than or equal to 38 and less than or equal to 60; and
(4) the first surface of the first chromium layer and the second surface of the second chromium layer both have a resistivity of 1.72 [ mu ] omega-cm to 2.25 [ mu ] omega-cm.
Accordingly, the electrolytic copper foils of examples 1 to 11 still had good weather resistance without discoloration after the lay-out test. On the contrary, the electrolytic copper foils of comparative examples 1 to 11 could not simultaneously have the above-mentioned characteristics (1) to (4) because the process parameters of comparative examples 1 to 11 were not properly controlled in the production process, and thus some of the electrolytic copper foils (comparative examples 1, 2, 6, 11) still had a problem of discoloration, indicating that these electrolytic copper foils had a problem of poor weather resistance, and were not expected to be applicable to lithium ion batteries.
Table 2: results of electrolytic copper foils of examples 1 to 11(E1 to E11) and comparative examples 1 to 11(C1 to C11) measured through test examples 1 to 7
Figure GDA0003217071480000101
Test example 6: adhesion strength
The first and second surfaces of the electrolytic copper foil of the above examples 1 to 11 may be further coated with a negative electrode slurry to make a negative electrode for a lithium ion battery.
Specifically, the negative electrode can be prepared by the following steps: first, an anode slurry was prepared in which an active composition comprising 93.9 wt% of mesolith toner (MGP) and 1 wt% of conductive carbon black powder (Super) was mixed in a ratio of 60g of a solvent (N-methylpyrrolidone (NMP)) per 100g of the active composition
Figure GDA0003217071480000111
) 5 wt% solvent binder (polyvinylidene fluoride, PVDF 6020) and 0.1 wt% oxalic acid.
Then, coating the negative electrode slurry on the first surface and the second surface of the electrolytic copper foil at the speed of 5m/min until the thickness of each of the first surface and the second surface of the electrolytic copper foil reaches 200 mu m, and drying in an oven at 160 ℃; rolling the mixture by using a rolling machine under the conditions that the rolling speed is 1m/min and the pressure is 3000 pounds per square inch (psi), so that the negative electrode slurry is rolled to the density of 1.5 grams per cubic centimeter (g/cm)3) And obtaining the cathode. Here, the roller size of the roller was 250mm × 250mm, the hardness of the roller was 62 to 65HRC, and the roller material was high carbon chromium bearing steel (SUJ 2).
Cutting the cathode prepared by the method into the size of 200mm multiplied by 20mm to obtain a sample to be detected; similarly, the electrolytic copper foils of comparative examples 1 to 11 were also prepared into samples to be tested by the above-described method, as a control for evaluating the adhesive strength between the electrolytic copper foils of examples 1 to 11 and the negative electrode active material.
Finally, 3M Scotch (R) Magic was usedTMRespectively sticking adhesive tapes on the first surface and the second surface of each sample to be tested by using IMADA tensile machine(instrument model: DS2-20N) the adhesion strength between each of the first and second surfaces of the electrolytic copper foil and the active material in each of the samples to be tested was analyzed, and the results thereof are also shown in Table 2.
Test example 7: cycle life
In addition to the negative electrode described in test example 6, the electrolytic copper foils of examples 1 to 11 were used as negative electrodes, and then, lithium ion batteries were further prepared.
Specifically, a negative electrode of a lithium ion battery was obtained according to the method of test example 6 described above. In addition, a positive electrode slurry was prepared in which an active composition contained 89 wt% of LiCoO in a proportion of 195g of a solvent (NMP) per 100g of the active composition was mixed25 wt% of flaked graphite (KS 6), 1 wt% of conductive carbon black powder (Super)
Figure GDA0003217071480000112
) 5% by weight of polyvinylidene fluoride (PVDF 6020). And then coating the positive electrode slurry on an aluminum foil until the thickness of the aluminum foil reaches 250 mu m, and drying in an oven at 160 ℃ to obtain the positive electrode. Then, the positive electrodes and the negative electrodes are alternately stacked, a microporous isolation film (model Celgard 2400, manufactured by Celgard corporation) is sandwiched between the positive electrodes and the negative electrodes, and then the positive electrodes and the negative electrodes are placed in a pressing mold filled with electrolyte (model LBC322-01H, purchased from new aegium technologies ltd) to form a laminated lithium ion battery in a sealing manner, namely the sample to be tested for subsequent evaluation of cycle life performance. The size of the laminated lithium ion battery is 41mm multiplied by 34mm multiplied by 53 mm. Similarly, the electrodeposited copper foils of comparative examples 1 to 11 were also prepared into test samples of lithium ion batteries by the above-described methods, as a control for evaluating cycle life performance when the electrodeposited copper foils of the above-described examples are applied to lithium ion batteries.
In the analysis of the cycle life of the lithium ion battery, each sample to be tested was subjected to a charge-discharge cycle test at a temperature of 55 ℃ in a constant current-constant voltage (CCCV) charge mode and a Constant Current (CC) discharge mode under conditions of a charge voltage of 4.2 volts (V), a charge current of 5C, a discharge voltage of 2.8V, and a discharge current of 5C.
In the present test example, the number of charge and discharge cycles performed when the capacity of the lithium ion battery was decreased to 80% of the initial capacity was defined as the cycle life of the lithium ion battery. The results of cycle life tests of lithium ion batteries manufactured by the electrolytic copper foils of each example and comparative example are also shown in table 2.
Discussion of Experimental results
According to the experimental results shown in table 2, since the electrolytic copper foils of examples 1 to 11 have the above characteristics (1) to (4), these electrolytic copper foils can not only obtain good weather resistance, but also obtain appropriate adhesion strength with the negative active material when they are applied to the lithium ion battery, and the cycle life of the lithium ion battery including them can be increased to more than 800 times, even as high as 1000 times to 1400 times.
On the contrary, the electrodeposited copper foils of comparative examples 1 to 11 cannot simultaneously satisfy the above-mentioned characteristics (1) to (4), so that the electrodeposited copper foils cannot simultaneously satisfy good weather resistance and obtain appropriate adhesion strength with the negative electrode active material, and the cycle life of the lithium ion batteries including the electrodeposited copper foils cannot be as long as 800 times. As shown in table 2, the electrolytic copper foils of comparative examples 1, 2, 6, and 11 were judged to be unsuitable for use in lithium ion batteries in advance because of insufficient weather resistance, and the results of cycle life tests are not shown in table 2; while comparative example 9 has no problem of insufficient weather resistance, it has been previously judged as unsuitable for use in a lithium ion battery because of its significantly insufficient adhesive strength (less than 0.2kg) with a negative electrode active material, and thus table 2 does not show the cycle life test results of the electrolytic copper foil of comparative example 9 applied to a lithium ion battery; in contrast, in comparative example 10, although there is no problem of insufficient weather resistance, the cycle life of the lithium ion battery is not improved even less than 600 times because the adhesion strength between the electrolytic copper foil of comparative example 10 and the negative electrode active material is too high.
Further analyzing the experimental results of table 2, it can be seen that the contact angles between the first surface and the second surface of the electrolytic copper foil and the 0.1 wt% aqueous oxalic acid solution affect the adhesion strength between the electrolytic copper foil and the negative active material, and further affect the cycle life of the lithium ion battery including the electrolytic copper foil. Taking the results of the electrolytic copper foils of comparative examples 9 to 11 as an example, when the contact angles between the first surface, the second surface and the 0.1 wt% aqueous oxalic acid solution exceed 15 degrees to 50 degrees, the electrolytic copper foils of comparative examples 9 and 10 have problems of too low or too high adhesion strength to the negative electrode active material, respectively, while the electrolytic copper foil of comparative example 11 has a disadvantage of significantly insufficient weather resistance.
Furthermore, the chromium adhesion amount of the first chromium layer and the second chromium layer in the electrolytic copper foil affects the weather resistance and resistivity of the electrolytic copper foil, and the resistivity of the electrolytic copper foil is affected when the electrolytic copper foil is oxidized, and the cycle life performance of the lithium ion battery is even deteriorated. Taking the results of the electrodeposited copper foils of comparative examples 1, 2, 4 and 5 as examples, when the amount of chromium adhesion of the first chromium layer and the second chromium layer exceeded 15. mu.g/dm2To 50. mu.g/dm2In the range of (3), the electrolytic copper foils of comparative examples 1 and 2 have a disadvantage of remarkably insufficient weather resistance, while the electrolytic copper foils of comparative examples 4 and 5 have a problem of poor cycle life performance when applied to lithium ion batteries.
In addition, the brightness of the electrolytic copper foil affects the cycle life performance of the lithium ion battery including the electrolytic copper foil. Taking the results of the electrolytic copper foils of comparative examples 6 to 8 and 11 as examples, when the brightness of the first surface of the electrolytic copper foil exceeds the range of 17.5 to 40 and/or the brightness of the second surface exceeds the range of 38 to 60, the electrolytic copper foils of comparative examples 6 and 11 both had a problem of poor weather resistance, while the electrolytic copper foils of comparative examples 7 and 8 applied to lithium ion batteries had a problem of poor cycle life performance.
In addition, the electrical resistivity of the first surface of the first chromium layer and the electrical resistivity of the second surface of the second chromium layer of the electrolytic copper foil are also related to the cycle life of the lithium ion battery. When the specific resistance of the first surface of the first chrome layer and the second surface of the second chrome layer of the electrolytic copper foil is out of the range of 1.72 μ Ω · cm to 2.25 μ Ω · cm, the cycle life performance of the lithium ion battery including the electrolytic copper foils of comparative examples 3, 4, 5, and 10 is not satisfactory, and it is seen that the cycle life performance of the lithium ion battery is deteriorated also when the specific resistance of the first surface of the first chrome layer and the second surface of the second chrome layer of the electrolytic copper foil is excessively high.
On the other hand, comparing the characteristics of the electrolytic copper foils of examples 1 to 11, it was found that when the lightness of the first surface of the electrolytic copper foil falls within the range of 25 to 40 and the lightness of the second surface falls within the range of 45 to 60, the cycle life of the lithium ion battery comprising the electrolytic copper foils of examples 1 to 6 and 9 to 11 can be further increased to 1100 times or more, being superior to the cycle life performance of the lithium ion battery comprising the electrolytic copper foils of examples 7 and 8.
In addition, when the contact angle between the first surface of the electrolytic copper foil and the 0.1 wt% aqueous oxalic acid solution is greater than or equal to 15 degrees and less than 40 degrees and the contact angle between the second surface and the 0.1 wt% aqueous oxalic acid solution is greater than or equal to 15 degrees and less than or equal to 40 degrees, the adhesion strength between the first surface, the second surface and the anode active material of the electrolytic copper foils of examples 2, 4, 6, 8, 10 can be further optimized.
In summary, the present invention adjusts and controls the electrolytic copper foil to have the characteristics (1) to (4) at the same time, and can specifically improve the weather resistance of the electrolytic copper foil and the adhesion strength between the electrolytic copper foil and the active material, thereby optimizing the cycle life performance of the lithium ion battery including the electrolytic copper foil, and further improving the performance of the lithium ion battery including the electrolytic copper foil.

Claims (10)

1. An electrolytic copper foil comprising:
a copper layer comprising deposition and roll surfaces on opposite sides;
a first chromium layer formed on a deposition surface of the copper layer, the first chromium layer including a first surface opposite to the deposition surface, the first chromium layer having a chromium adhesion amount of 15 [ mu ] g/dm or more2And less than or equal to 50 [ mu ] g/dm2And a contact angle between the first surface and 0.1 weight percent aqueous oxalic acid solution is greater than or equal to 15 degrees and less than or equal to 50 degrees, a lightness of the first surface is greater than or equal to 17.5 and less than or equal to 40, and a resistivity of the first surface of the first chromium layer is greater than or equal to 1.72 [ mu ] Ω -cm and less than or equal to 2.25 [ mu ] Ω -cm; and
a second chromium layer formed on a roll surface of the copper layer, the second chromium layerComprising a second surface opposite to the surface of the roller, the second chromium layer having a chromium adhesion of 15 [ mu ] g/dm or more2And less than or equal to 50 [ mu ] g/dm2And a contact angle between the second surface and 0.1 weight percent aqueous oxalic acid solution is greater than or equal to 15 degrees and less than or equal to 50 degrees, a lightness of the second surface is greater than or equal to 38 and less than or equal to 60, and a resistivity of the second surface of the second chromium layer is greater than or equal to 1.72 [ mu ] Ω & cm and less than or equal to 2.25 [ mu ] Ω & cm.
2. The electrolytic copper foil according to claim 1, wherein a chromaticity a value of the first surface is 3 or more and 12 or less, and a chromaticity a value of the second surface is 8 or more and 16 or less.
3. The electrolytic copper foil according to claim 1, wherein a chromaticity b value of the first surface is greater than or equal to 1.3 and less than or equal to 18, and a chromaticity b value of the second surface is greater than or equal to 8 and less than or equal to 16.
4. The electrolytic copper foil according to claim 2, wherein a chromaticity b value of the first surface is greater than or equal to 1.3 and less than or equal to 18, and a chromaticity b value of the second surface is greater than or equal to 8 and less than or equal to 16.
5. The electrolytic copper foil according to any one of claims 1 to 4, wherein the lightness of the first surface is greater than or equal to 25 and less than or equal to 40, and the lightness of the second surface is greater than or equal to 45 and less than or equal to 60.
6. The electrolytic copper foil according to any one of claims 1 to 4, wherein a contact angle between the first surface and 0.1 weight percent aqueous oxalic acid solution is greater than or equal to 15 degrees and less than 40 degrees, and a contact angle between the second surface and 0.1 weight percent aqueous oxalic acid solution is greater than or equal to 15 degrees and less than or equal to 40 degrees.
7. The electrolytic copper foil of claim 6, wherein a contact angle between the first surface and 0.1 weight percent aqueous oxalic acid solution is greater than or equal to 15 degrees and less than or equal to 30 degrees, and a contact angle between the second surface and 0.1 weight percent aqueous oxalic acid solution is greater than or equal to 15 degrees and less than or equal to 30 degrees.
8. The electrolytic copper foil of claim 6, wherein the lightness of the first surface is greater than or equal to 25 and less than or equal to 40, and the lightness of the second surface is greater than or equal to 45 and less than or equal to 60.
9. An electrode for a lithium ion battery comprising the electrolytic copper foil of any one of claims 1 to 8.
10. A lithium ion battery comprising the electrode of claim 9.
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